The Reds finished fourth last term but after a summer of serious investment, Jurgen Klopp's charges are expected to mount a credible challenge for the title this time around.
Since the end of last season, it has been all change at West Ham as Manuel Pellegrini has replaced David Moyes in the dugout and has made a raft of summer signings in a bid to bolster his squad.
The Reds were reliable on home turf last term, ending the Premier League season unbeaten at Anfield, and it is little surprise that bet365 offer just 1/5 (1.20) that the men from Merseyside kick off with a win.
Alisson, Fabinho and Naby Keita could all make their competitive debuts, but Xherdan Shaqiri may have to settle for a place on the substitutes' bench this weekend.
Virgil van Dijk is the Reds' only fully-fit central defender, with Joe Gomez providing the latest injury concern after missing Tuesday's final friendly fixture with Torino.
West Ham's new faces Andriy Yarmolenko, Felipe Anderson, Issa Diop, Lukasz Fabianski, Fabian Balbuena, Jack Wilshere and Ryan Fredericks are all in contention to start for the visitors.
Liverpool scored eight goals in two Premier League matches against the Hammers last term, winning 4-1 on both occasions, and bet365 go just 4/9 (1.44) that there are more than two goals in this game.
Much was made of Liverpool's purported lack of defensive discipline last term, but the Reds closed their Premier League campaign with five successive shutouts at Anfield, winning four of those matches.
Klopp's charges can show their steely side once again here and, so, bet365's 20/21 (1.95) quote for Liverpool to win to nil could represent good value for punters ahead of Sunday's showdown.
Odds correct at time of writing. Please gamble responsibly.